Oxime ester compound and photopolymerization initiator containing the same

ABSTRACT

An oxime ester compound represented by general formula (I): 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , and R 3  each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 , or CN; R 11 , R 12 , and R 13  each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 4  and R 5  each independently represent R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN, a halogen atom, or a hydroxyl group; and a and b each independently represent 0 to 3.

TECHNICAL FIELD

This invention relates to a novel oxime ester compound useful as aphotopolymerization initiator in a photosensitive composition, aphotopolymerization initiator containing the compound as an activeingredient, and a photosensitive composition containing a polymerizablecompound having an ethylenically unsaturated bond and thephotopolymerization initiator.

BACKGROUND ART

A photosensitive composition contains a polymerizable compound having anethylenically unsaturated bond and a photopolymerization initiator. Aphotosensitive composition polymerizes to cure on being irradiated withlight of 405 nm or 365 nm and is used in photo-curing inks,photosensitive printing plate precursors, and various photoresists.

Patent documents 1 to 8 listed below propose using an O-acyl oximecompound having a carbazolyl structure as a photopolymerizationinitiator of a photosensitive composition. However, the known O-acyloxime compounds are not sufficiently satisfactory particularly insensitivity.

Patent document 1: JP 2001-302871A

Patent document 2: JP 2004-534797A

Patent document 3: JP 2005-25169A

Patent document 4: JP 2005-128483A

Patent document 5: JP 2005-242279A

Patent document 6: JP 2005-242280A

Patent document 7: JP 2006-16545A

Patent document 8: Japanese Patent 3754065

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention

The problem to be solved is that there has been no photopolymerizationinitiator having satisfactory sensitivity.

Accordingly, an object of the invention is to provide a highly sensitivephotopolymerization initiator that efficiently absorbs light of longwavelength, e.g., 405 nm or 365 nm, to be activated.

Means for Solving the Problem

The above object is accomplished by the provision of an oxime estercompound represented by general formula (I) below and aphotopolymerization initiator containing the oxime ester compound as anactive ingredient.

[Formula 1]

wherein R¹, R², and R³ each independently represent R¹¹, OR¹¹, COR¹¹,SR¹¹, CONR¹²R¹³, or CN; R¹¹, R¹², and R¹³ each independently represent ahydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl grouphaving 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbonatoms, or a heterocyclic group having 2 to 20 carbon atoms, in which thealkyl group, aryl group, arylalkyl group, and heterocyclic group mayhave their hydrogen atom substituted with OR²¹, COR²¹, SR²¹, NR²²R²³,CONR²²R²³, —NR²²—OR²³, —NCOR²²—OCOR²³, —C(═N—OR²¹)—R²²,—C(═N—OCOR²¹)—R²², CN, a halogen atom, —CR²¹═CR²²R²³, —CO—CR²¹═CR²²R²³,a carboxyl group, or an epoxy group; R²¹, R²², and R²³ eachindependently represent a hydrogen atom, an alkyl group having 1 to 20carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkylgroup having 7 to 30 carbon atoms, or a heterocyclic group having 2 to20 carbon atoms; the methylene units of the alkylene moiety of thesubstituents represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³ may beinterrupted by an unsaturated linkage, an ether linkage, a thioetherlinkage, an ester linkage, a thioester linkage, an amide linkage, or aurethane linkage at 1 to 5 sites thereof; the alkyl moiety of thesubstituents represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³ may bebranched or cyclic; an alkyl terminal of the substituents represented byR¹¹, R¹², R¹³, R²¹, R²², and R²³ may have an unsaturated bond; R¹² andR¹³, and R²² and R²³ may be connected to each other form a ring; R³ maybe taken together with a neighboring benzene ring; R⁴ and R⁵ eachindependently represent R¹¹, OR¹¹, SR¹¹, COR¹¹, CONR¹²R¹³, NR¹²COR¹¹,OCOR¹¹, COOR¹¹, SCOR¹¹, OCSR¹¹, COSR¹¹, CSOR¹¹, CN, a halogen atom, or ahydroxyl group; and a and b each independently represent 0 to 3.

The invention also provides a photosensitive composition containing thephotopolymerization initiator and a polymerizable compound having anethylenically unsaturated bond.

The invention also provides an alkali-developable photosensitive resincomposition containing the photopolymerization initiator and analkali-developable compound having an ethylenically unsaturated bond.

The invention also provides a colored alkali-developable photosensitiveresin composition comprising the alkali-developable photosensitive resincomposition and a colorant.

BEST MODE FOR CARRYING OUT THE INVENTION

The oxime ester compound of the invention and a photopolymerizationinitiator containing the compound as an active ingredient will bedescribed in detail.

The oxime ester compound according to the invention embraces geometricisomers based on the double bond of oxime. Either of the isomers isuseful. The general formula (I) and the formulae of specific examples ofthe compounds given later each represent either one of the isomers or amixture of the isomers, not being limited to the isomeric structureshown.

In general formula (I), examples of the alkyl group as represented byR¹¹, R¹², R¹³, R²¹, R²², and R²³ include methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, t-butyl, amyl, isoamyl, t-amyl,hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl,decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl,eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, vinyl, allyl,butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl,pentyloxyethyl, octyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl,propoxyethoxyethyl, methoxypropyl, and 2-methoxy-1-methylethyl. Examplesof the aryl group as represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl,anthryl, phenanthryl; and phenyl, biphenylyl, naphthyl or anthrylsubstituted with at least one of the above recited alkyl groups.Examples of the arylalkyl group as represented by R¹¹, R¹², R¹³, R²¹,R²², and R²³ include benzyl, chlorobenzoyl, α-methylbenzyl,α,α-dimethylbenzyl, phenylethyl, and phenylethenyl. The heterocyclicgroup as represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³ is preferably a5- to 7-membered heterocyclic group, including pyridyl, pyrimidyl,furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl,tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl,isothiazolidyl, oxazolidyl, isooxazolidyl, piperidyl, piperazyl, andmorpholinyl. Examples of the ring formed by connecting R¹² and R¹³, thering formed by connecting R²² and R²³, and the ring formed by connectingR³ and a neighboring benzene ring include 5- to 7-membered rings, suchas cyclopentane, cyclohexane, cyclopentene, benzene, piperidine,morpholine, lactone, and lactam rings. Examples of the halogen atom as asubstituent of R¹¹, R¹², R¹³, R²¹, R²², and R²³ and the halogen atomrepresented by R⁴ and R⁵ include fluorine, chlorine, bromine, andiodine.

The methylene units of the alkylene moiety of the above describedsubstituents may be interrupted by an unsaturated linkage, an etherlinkage, a thioether linkage, an ester linkage, a thioester linkage, anamido linkage, or a urethane linkage at 1 to 5 sites. The interruptinglinking groups may be the same or different. Two or more interruptinglinking groups may be continued to each other, if possible. The alkylmoiety of the above described substituents may be branched or cyclic,and the alkyl terminal of the substituents may have an unsaturated bond.

Preferred of the oxime ester compounds of general formula (I) accordingto the invention are those in which R¹ is an alkyl group having 11 to 20carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkylgroup having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20carbon atoms, OR¹¹, COR¹¹, SR¹¹, CONR¹²R¹³, or CN and those in which R³is an alkyl group having 1 to 12 carbon atoms and interrupted by anether linkage or an ester linkage at 1 to 5 sites, an alkyl group having13 to 20 carbon atoms, OR¹¹, COR¹¹, SR¹¹, CONR¹²R¹³, or CN. Particularlypreferred are those in which R¹ is an alkyl group having 11 to 20 carbonatoms or an aryl group having 6 to 30 carbon atoms, or R³ is a branchedalkyl group having 8 or more carbon atoms the methylene units of whichmay be interrupted by an ether linkage or an ester linkage at 1 to 5sites; those in which R³ is an alkyl group having 13 or more carbonatoms the methylene units of which may be interrupted by an etherlinkage or an ester linkage at 1 to 5 sites; those in which R³ is analkyl group interrupted by an ether linkage at 1 to 5 sites; and thosein which R³ is an alkyl group interrupted by an ester linkage at 1 to 5sites. These preferred compounds are easy to synthesize and show highsensitivity.

When used as a photopolymerization initiator, they dissolve in propyleneglycol-1-monomethyl ether-2-acetate or cyclohexanone as a solvent to aconcentration of 1% by mass or higher, to satisfy the requirement as aphotopolymerization initiator. The solubility measurement is preferablymade at 20° to 30° C.

The oxime ester compound of the invention may be dimerized at R¹ or R²to provide a compound represented by formulae shown below:

Examples of the preferred oxime ester compounds of general formula (I)include, but are not limited to, compound Nos. 1 through 71 below.

The oxime ester compound of general formula (I) is prepared by, forexample, the following process in accordance with reaction scheme:

A nitrocarbazole compound 1 and an acid chloride 2 are allowed to reactin the presence of zinc chloride to give an acylated compound 3. Theacylated compound 3 is allowed to react with hydroxylamine hydrochloridein the presence of DMF to give an oxime compound 4. The oxime compound 4is allowed to react with an acid anhydride 5 or an acid chloride 5′ toyield an oxime ester compound of general formula

(I).

The oxime ester compound of the invention is useful as an initiator forphotopolymerization of a polymerizable compound having an ethylenicallyunsaturated bond.

The photosensitive composition according to the invention will then bedescribed. The photosensitive composition of the invention contains aphotopolymerization initiator having the oxime ester compound as anactive ingredient, an ethylenically unsaturated polymerizable compound,and, if desired, an inorganic compound and/or a colorant, and otheroptional components such as a solvent.

Any ethylenically unsaturated polymerizable compound that has been usedin a photosensitive composition can be used in the invention. Examplesinclude unsaturated aliphatic hydrocarbons, such as ethylene, propylene,butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidenefluoride, and tetrafluoroethylene; a polymer having a carboxyl group anda hydroxyl group at both terminals, such as (meth)acrylic acid,α-chloroacrylic acid; itaconic acid, maleic acid, citraconic acid,fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylaceticacid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid,trimellitic acid, pyromellitic acid,2,2′,3,3′-benzophenonetetracarboxylic acid,3,3,4,4′-benzophenonetetracarboxylic acid,mono[2-(meth)acryloyloxyethyl]succinate,mono[2-(meth)acryloyloxyethyl]phthalate, a mono(methacrylate) andω-carboxypolycaprolactone mono(meth)acrylate; unsaturated polybasicacids such as hydroxyethyl (meth)acrylate malate, hydroxypropyl(meth)acrylate malate, dicyclopentadiene malate, and a polyfunctional(meth)acrylate having one carboxyl group and two or more (meth)acryloylgroups; esters between an unsaturated monobasic acid and a polyhydricalcohol or a polyhydric phenol, such as 2-hydroxyethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, compound Nos.72 to 75 shown below, methyl (meth)acrylate, butyl (meth)acrylate,isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl(meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate,isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate,methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate,dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate,dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate,poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate,ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuryl(meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate,1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,trimethylolethane tri(meth)acrylate, trimethylolpropanetri(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, pentaerythritolpenta(meth)acrylate, pentaerythritol tetra(meth)acrylate,pentaerythritol tri(meth)acrylate, tricyclodecanedimethyloldi(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester(meth)acrylate oligomers; metal salts of unsaturated polybasic acids,such as zinc (meth)acrylate and magnesium (meth)acrylate; unsaturatedpolybasic acid anhydrides, such as maleic anhydride, itaconic anhydride,citraconic anhydride, methyltetrahydrophthalic anhydride,tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydrides,5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylicacid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydrideadducts, dodecenylsuccinic anhydride, and methylhymic anhydride; amidesformed between an unsaturated monobasic acid and a polyfunctional amine,such as (meth)acrylamide, methylenebis(meth)acrylamide,diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide,α-chloroacrylamide, and N-2-hydroxyethyl (meth)acrylamide; unsaturatedaldehydes, such as acrolein; unsaturated nitriles, such as(meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, andallyl cyanide; unsaturated aromatic compounds, such as styrene,4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene,4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid,vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid,vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether; unsaturatedketones, such as methyl vinyl ketone; unsaturated amine compounds, suchas vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine;vinyl alcohols, such as allyl alcohol and crotyl alcohol; vinyl ethers,such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether,isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides, suchas maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes,such as indene and 1-methylindene; aliphatic conjugated dienes, such as1,3-butadiene, isoprene, and chloroprene; macromonomers having amono(meth)acryloyl group at the terminal of a polymeric molecular chain,such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxanes; vinyl chloride, vinylidene chloride,divinyl succinate, diallyl phthalate, triallyl phosphate, triallylisocyanurate, vinyl thioether, vinylimidazole, vinyloxazoline,vinylcarbazole, vinylpyrrolidone, vinylpyridine, vinylurethane compoundsformed between a hydroxyl-containing vinyl monomer and a polyisocyanatecompound, and vinylepoxy compounds formed between a hydroxyl-containingvinyl monomer and a polyepoxy compound. Of these ethylenicallyunsaturated polymerizable compounds, a (mono)methacrylate of a polymerhaving a carboxyl group and a hydroxyl group at both terminals, apolyfunctional (meth)acrylate having one carboxyl group and two or more(meth)acryloyl groups, and an ester between an unsaturated monobasicacid and a polyhydric alcohol or polyhydric phenol are suited to bepolymerized by using the photopolymerization initiator containing theoxime ester compound of the invention as an active ingredient.

The polymerizable compounds may be used either individually or as amixture of two or more thereof. The two or more polymerizable compoundsto be used in combination may be in the form of a copolymer previouslyprepared therefrom.

When the ethylenically unsaturated polymerizable compound is anethylenically unsaturated, alkali-developable compound, thephotosensitive composition of the invention serves as analkali-developable photosensitive resin composition. Examples of theethylenically unsaturated, alkali-developable compound include acrylicester copolymers, phenol and/or cresol novolak epoxy resins,polyphenylmethane epoxy resins having two or more epoxy groups, andresins obtained by causing an epoxy compound, such as a compoundrepresented by general formula (II) below, and an unsaturated monobasicacid to react with each other and causing the resulting reaction productto react with a polybasic acid anhydride. Preferred of them are resinsobtained by causing an epoxy compound, such as a compound represented bygeneral formula (II) below, and an unsaturated monobasic acid to reactwith each other and causing the resulting product to react with apolybasic acid anhydride. The ethylenically unsaturated,alkali-developable compound preferably contains 0.2 to 1.0 equivalentsof an unsaturated group.

wherein X¹ represents a single bond, a methylene group, ahalogen-substituted or unsubstituted alkylidene group having 1 to 4carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbonatoms, O, S, SO₂, SS, SO, CO, OCO, or a substituent represented by[formula 16] or [formula 17] shown below; R⁴¹, R⁴², R⁴³, and R⁴⁴ eachindependently represent a hydrogen atom, a halogen-substituted orunsubstituted alkyl group having 1 to 5 carbon atoms, ahalogen-substituted or unsubstituted alkoxy group having 1 to 8 carbonatoms, a halogen-substituted or unsubstituted alkenyl group having 2 to5 carbon atoms, or a halogen atom; and m represents an integer of 0 to10.

wherein Y¹ represents a hydrogen atom, a phenyl group which may besubstituted with an alkyl group having 1 to 10 carbon atoms or an alkoxygroup having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10carbon atoms; Z¹ represents a halogen-substituted or unsubstituted alkylgroup having 1 to 10 carbon atoms, a halogen-substituted orunsubstituted alkoxy group having 1 to 10 carbon atoms, ahalogen-substituted or unsubstituted alkenyl group having 2 to 10 carbonatoms, or a halogen atom; and d represents an integer of 0 to 5.

Examples of the unsaturated monobasic acid which is caused to react onthe epoxy compound include acrylic acid, methacrylic acid, crotonicacid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate,hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate,hydroxypropyl acrylate malate, and dicyclopentadiene malate. Examples ofthe polybasic acid anhydride that is caused to react after the reactionof the unsaturated monobasic acid include biphenyltetracarboxylic aciddianhydride, tetrahydrophthalic anhydride, succinic anhydride,biphthalic anhydride, maleic anhydride, trimellitic anhydride,pyromellitic anhydride, 2,2′,3,3′-benzophenonetetracarboxylic acidanhydride, ethylene glycol bisanhydrotrimellitate, glyceroltrisanhydrotrimellitate, hexahydrophthalic anhydride,methyltetrahydrophthalic anhydride, nadic anhydride, methylnadicanhydride, trialkyltetrahydrophthalic anhydrides, hexahydrophthalicanhydride,5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylicacid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydrideadducts, dodecenylsuccinic anhydride, and methylhymic anhydride.

The epoxy compound and the unsaturated monobasic acid are preferablyused in such a molar ratio that results in the formation of an epoxyadduct having 0.1 to 1.0 carboxyl group of the unsaturated monobasicacid added per epoxy group of the epoxy compound. The polybasic acidanhydride is preferably used in such a molar ratio as to provide 0.1 to1.0 acid anhydride structure per hydroxyl group of the resulting epoxyadduct.

The reactions of the epoxy compound, unsaturated monobasic acid, andpolybasic acid anhydride are carried out in a usual manner.

In order to improve developability of the alkali-developablephotosensitive resin composition, either colored or not colored, theacid value of the ethylenically unsaturated alkali-developable compoundmay be adjusted by using a mono- or polyfunctional epoxy compound incombination with the ethylenically unsaturated, alkali-developablecompound. It is preferred that the solid content of the ethylenicallyunsaturated, alkali-developable compound to have an acid value of 5 to120 mg-KOH/g. The amount of the mono- or polyfunctional epoxy compoundto be used is preferably chosen so as to satisfy the above recited rangeof acid value.

Examples of the monofunctional epoxy compound include glycidylmethacrylate, methyl glycidyl ether, ethyl glycidyl ether, propylglycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutylglycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexylglycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonylglycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecylglycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether,pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexylglycidyl ether, allyl glycidyl ether, propargyl glycidyl ether,p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidylether, p-butylphenyl glycidyl ether, cresyl glycidyl ether,2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzylglycidyl ether, p-cumylphenyl glycidyl ether, trimethyl glycidyl ether,2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseedoil, glycidyl butyrate, vinylcyclohexene monoxide,1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyreneoxide, cyclohexene oxide, propylene oxide, and compound Nos. 76 and 77below.

The polyfunctional epoxy compound is preferably at least one compoundselected from the group consisting of bisphenol epoxy compounds andglycidyl ethers.

Using at least one of them is effective in providing a (colored) alkalidevelopable photosensitive resin composition having further improvedcharacteristics. Examples of the bisphenol epoxy compounds include theepoxy compounds represented by general formula (II) and others includinghydrogenated bisphenol epoxy compounds. Examples of the glycidyl ethersinclude ethylene glycol diglycidyl ether, propylene glycol diglycidylether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether,2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycoldiglycidyl ether, triethylene glycol diglycidyl ether, tetraethyleneglycol diglycidyl ether, hexaethylene glycol diglycidyl ether,1,4-cyclohexanedimethanol diglycidyl ether,1,1,1-tri(glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane,1,1,1-tri(glycidyloxymethyl)methane, and1,1,1,1-tetra(glycidyloxymethyl)methane.

Other useful polyfunctional epoxy compounds include novolak epoxycompounds, such as phenol novolak epoxy compounds, biphenyl novolakepoxy compounds, cresol novolak epoxy compounds, bisphenol A novolakepoxy compounds, and dicyclopentadiene novolak epoxy compounds;alicyclic epoxy compounds, such as3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate,3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters, such as diglycidylphthalate, diglycidyl tetrahydrophthalate, and glycidyl dimerate;glycidylamines, such as tetraglycidyl diaminodiphenylmethane,triglycidyl p-aminophenol, and N,N-diglycidylaniline; heterocyclic epoxycompounds, such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidylisocyanurate; dioxide compounds, such as dicyclopentadiene dioxide;naphthalene epoxy compounds, triphenylmethane epoxy compounds, anddicyclopentadiene epoxy compounds.

The amount of the photopolymerization initiator to be used in thephotosensitive composition of the invention is preferably, but notlimited to, 1 to 70 parts, more preferably 1 to 50 parts, even morepreferably 5 to 30 parts, by mass per 100 parts by mass of theethylenically unsaturated polymerizable compound.

In the case when the photosensitive composition is contemplated to be a(colored) alkali developable photosensitive resin composition, thecontent of the ethylenically unsaturated, alkali developable compound inthe composition is preferably 1 to 20%, more preferably 3 to 12%, bymass.

The photosensitive composition of the invention may optionally contain asolvent. Usually, solvents capable of dissolving or dispersing the abovedescribed components (such as the oxime ester compound of the inventionand the ethylenically unsaturated polymerizable compound) are used wherenecessary. Such solvents include ketones, e.g., methyl ethyl ketone,methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone,methyl isobutyl ketone, and cyclohexanone; ethers, such as ethyl ether,dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, anddipropylene glycol dimethyl ether; esters, such as methyl acetate, ethylacetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate;cellosolve solvents, such as ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, and propylene glycol-1-monoethylether-2-acetate;; alcohols, such as methanol, ethanol, isopropylalcohol, n-propanol, isobutanol, n-butanol, and amyl alcohol; ethers,such as ethylene glycol monomethyl acetate, ethylene glycol monoethylacetate, and propylene glycol methyl acetate; BTX solvents (benzene,toluene, xylene, etc.); aliphatic hydrocarbons, such as hexane, heptane,octane, and cyclohexane; terpene hydrocarbon oils, such as turpentineoil, D-limonene, and pinene; paraffinic solvents, such as mineralspirit, Swazol #310 (available from Cosmo Matsuyama Oil Co., ltd.), andSolvesso #100 (available from Exxon Chemical); halogenated aliphatichydrocarbons, such as carbon tetrachloride, chloroform,trichloroethylene, methylene chloride, and 1,2-dichloroethane;halogenated aromatic hydrocarbons, such as chlorobenzene; carbitolsolvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile,carbon disulfide, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and water. These solvents may be used either individually oras a mixture of two or more thereof.

Preferred of them are ketones and cellosolve solvents, particularlypropylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and so onin view of providing good compatibility between a resist and aphotopolymerization initiator in a photosensitive composition.

The photosensitive composition may further contain an inorganiccompound. Examples of the inorganic compound include metal oxides, suchas nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide,magnesium oxide, calcium oxide, potassium oxide, silica, and alumina;layered clay minerals, Milori blue, calcium carbonate, magnesiumcarbonate, cobalt compounds, manganese compounds, glass powder, mica,talc, kaolin, ferrocyanides, various metal sulfates, sulfides,selenides, aluminum silicate, calcium silicate, aluminum hydroxide,platinum, gold, silver, and copper. Preferred of them are titaniumoxide, silica, layered clay minerals, and silver. The inorganic compoundcontent in the photosensitive composition is preferably 0.1 to 50 parts,more preferably 0.5 to 20 parts, by mass per 100 parts by mass of theethylenically unsaturated polymerizable compound. The inorganiccompounds may be used either individually or in combination of two ormore thereof.

The inorganic compounds are used as, for example, a filler, anantireflection agent, an electrically conductive agent, a stabilizer, aflame retardant, a mechanical strength improving agent, a specificwavelength absorbing agent, an ink repellent agent, and the like.

The photosensitive composition of the invention, especially the alkalidevelopable photosensitive resin composition may further contain acolorant to be formulated into a colored photosensitive composition.Pigments, dyes, and naturally occurring dyes are used as a colorant. Thecolorants may be used either individually or as a mixture of two or morethereof.

The pigments may be either organic or inorganic, including nitrosocompounds, nitro compounds, azo compounds, diazo compounds, xanthenecompounds, quinoline compounds, anthraquinone compounds, coumarincompounds, phthalocyanine compounds, isoindolinone compounds,isoindoline compounds, quinacridone compounds, anthanthrone compounds,perynone compounds, perylene compounds, diketopyrrolopyrrole compounds,thioindigo compounds, dioxazine compounds, triphenylmethane compounds,quinophthalone compounds, and naphthalenetetracarboxylic acids; metalcomplex compounds, such as azo dyes, and cyanine dyes; lake pigments;carbon black species, such as furnace black, channel black, thermalblack, acetylene black, Ketjen black, and lamp black; the carbon blacksrecited which have been surface treated with an acid or an alkali;graphite, graphitized carbon black, activated carbon, carbon fiber,carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel,fullerene; aniline black, pigment black 7, titanium black; hydrophobicresins, chromium oxide green, Milori blue, cobalt green, cobalt blue,manganese compounds, ferrocyanides, phosphate ultramarine blue, Prussianblue, ultramarine, cerulean blue, viridian, emerald green, lead sulfate,lead yellow, zinc yellow, Bengal red (red iron (III) oxide), cadmiumred, synthetic iron black, and amber. The pigments may be used eitherindividually or as a mixture thereof.

Commercially available pigments may be used, including pigment red 1, 2,3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122,123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192,200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, and254; pigment orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59,60, 61, 62, 64, 65, and 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20,24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114,117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152,153, 154, 166, 168, 175, 180, and 185; pigment green 7, 10, and 36;pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61,62, and 64; and pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, and50.

Examples of the dyes include azo dyes, anthraquinone dyes, indigoiddyes, triarylmethane dyes, xanthene dyes, alizarine dyes, acridine dyes,stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes,indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. Themay be used as a mixture thereof.

The amount of the colorant to be added to the photosensitive compositionis preferably 50 to 350 parts, more preferably 100 to 250 parts, by massper 100 parts by mass of the ethylenically unsaturated polymerizablecompound.

The photosensitive composition may further contain other organic polymerin addition to the ethylenically unsaturated polymerizable compound toprovide a cured product with improved characteristics. Examples of theorganic polymer include polystyrene, polymethyl methacrylate, methylmethacrylate-ethyl acrylate copolymers, poly(meth)acrylic acid,styrene-(meth)acrylic acid copolymers, (meth)acrylic acid-methylmethacrylate copolymers, ethylene-vinyl chloride copolymers,ethylene-vinyl copolymers, polyvinyl chloride resins, ABS resins, nylon6, nylon 66, nylon 12, urethane resins, polycarbonate, polyvinylbutyral, cellulose esters, polyacrylamide, saturated polyesters, phenolresins, phenoxy resins, polyamide-imide resins, polyamic acid resins,and epoxy resins. Preferred of them are polystyrene, (meth)acrylicacid-methyl acrylate copolymers, and epoxy resins.

The amount of the other organic polymer is preferably 10 to 500 parts bymass per 100 parts by mass of the ethylenically unsaturatedpolymerizable compound.

The photosensitive composition may furthermore contain a monomer havingan unsaturated bond, a chain transfer agent, a surfactant, and so on.

Examples of the monomer having an unsaturated bond include2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate,n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearylacrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zincacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate,2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butylmethacrylate, t-butyl methacrylate, cyclohexyl methacrylate,trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate,dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate,pentaerythritol triacrylate, bisphenol A diglycidyl ether(meth)acrylate, bisphenol F diglycidyl ether (meth)acrylate, bisphenol Zdiglycidyl ether (meth)acrylate, and tripropylene glycoldi(meth)acrylate.

Examples of the chain transfer agent include mercapto compounds, such asthioglycolic acid, thiomalic acid, thiosalicylic acid,2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyricacid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid,3-[N-(2-mercaptoethyl)carbamoyl]propionic acid,3-[N-(2-mercaptoethyl)amino]propionic acid,N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid,3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol,3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol,mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole,2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid,trimethylolpropane tris(3-mercaptopropionate), and pentaerythritoltetrakis(3-mercaptopropionate); disulfide compounds obtained byoxidizing the recited mercapto compounds; and iodized alkyl compounds,such as iodoacetic acid, iodopropionic acid, 2-iodoethanol,2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid.

Examples of the surfactant include fluorine-containing surfactants, suchas perfluoroalkylphosphoric esters, perfluoroalkylcarboxylic acid salts;anionic surfactants, such as higher fatty acid alkali salts,alkylsulfonic acid salts, and alkylsulfuric acid salts; cationicsurfactants, such as higher amine halogenic acid salts and quaternaryammonium salts; nonionic surfactants, such as polyethylene glycol alkylethers, polyethylene glycol fatty acid esters, sorbitan fatty acidesters, and fatty acid monoglycerides; amphoteric surfactants, andsilicone surfactants. These surfactants may be used in combinationthereof.

If desired, the photosensitive composition may contain otherphotopolymerization initiator or sensitizer in addition to the oximeester compound of the invention. A combined use of otherphotopolymerization initiator can produce marked synergistic effects.

Any known photopolymerization initiators can be used in combination withthe oxime ester compound. Examples of such initiators includebenzophenone, phenyl biphenyl ketone, 1-hydroxy-1-benzoylcyclophexane,benzoin, benzyl dimethyl ketal,1-benzyl-1-dimethylamino-1-(4′-morpholinobenzoyl)propane,2-morpholyl-2-(4′-methylmercapto)benzoylpropane, thioxanthone,1-chloro-4-propoxythioxanthone, isopropylthioxanthone,diethylthioxanthone, ethylanthraquinone, 4-benzoyl-4′-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane,2-hydroxy-2-(4′-isopropyl)benzoylpropane,4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methylbenzoylformate, 1,7-bis(9′-acridinyl)heptane,9-n-butyl-3,6-bis(2′-morpholinoisobutyroyl)carbazole,2-methyl-4,6-bis(trichloromethyl)-s-triazine,2-phenyl-4,6-bis(trichloromethyl)-s-triazine,2-naphthyl-4,6-bis(trichloromethyl)-s-triazine,2,2-bis(2-chlorophenyl)-4,5,4′,5′-tetraphenyl-1,2′-biimidazole,4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone; N-1414,N-1717, N-1919, and PZ-408 (from ADEKA Corp.); Irgacure 369, Irgacure907, Irgacure OXE 01, and Irgacure OXE 02 (from Ciba SpecialtiesChemicals Corp.); benzoyl peroxide, and compounds represented by generalformulae (III) to (V) shown below. These photopolymerization initiatorscan be used either individually or in a combination of two or morethereof. The amount of the known photopolymerization initiator(s), ifused, is preferably equal to or less than the mass of the oxime estercompound of the invention.

wherein R¹ and R² are as defined for general formula (I); R⁶ has thesame meaning as R¹; Y² represents a halogen atom or an alkyl group; andn represents 0 to 5.

wherein R¹ and R² are as defined for general formula (I); R⁶, Y² and nare as defined for general formula (III); R^(′1), R^(′2), and R^(′6)have the same meaning as R¹; Y^(′2) has the same meaning as Y²; R⁷represents a diol residue or a dithiol residue; and Z² represents anoxygen atom or a sulfur atom.

wherein R¹ and R² are as defined for general formula (I); R⁶, Y², and nare as defined for general formula (III); Z³ represents an oxygen atom,a sulfur atom, or a selenium atom; A represents a heterocyclic group; prepresents an integer of 0 to 5; and q is 0 or 1.

If desired, the photosensitive composition of the present invention maycontain commonly used additives, including thermal polymerizationinhibitors (e.g., p-anisole, hydroquinone, pyrocatechol,t-butylcatechol, and phenothiazine), plasticizers, adhesionaccelerators, fillers, defoaming agents, leveling agents, surfacemodifiers, antioxidants, ultraviolet absorbers, dispersing acids,anti-coagulants, catalysts, effect accelerators, sensitizers,crosslinking agents, and thickeners.

The amounts of the optional components other than the ethylenicallyunsaturated polymerizable compound and the oxime ester compound, exceptthe above described other photopolymerization initiator, inorganicfiller, colorant, and solvent, in the photosensitive composition aredecided as appropriate to the use of the composition. Preferably, thetotal amount of the optional components is not more than 50 parts bymass per 100 parts by mass of the ethylenically unsaturatedpolymerizable compound.

The photosensitive composition of the invention is applied to asubstrate, such as soda glass, quartz glass, semiconductor substrates,metals, paper, or plastics. The method of application is not limited.Any known coating methods may be used, such as spin coating, rollcoating, bar coating, die coating, curtain coating, printing, anddipping. The photosensitive composition may be once applied to a carriersubstrate, such as a film, and then transferred to another substrate.

The photosensitive composition of the invention has unlimitedapplication. It finds use in, for example, photocuring paints orvarnishes, photocuring adhesives, printed boards; color filters forliquid crystal color display devices, such as TV monitors, PC monitors,personal digital assistances, and digital cameras; electrode materialsfor plasma display panels; powder coatings, printing inks, printingplates, adhesives, compositions for dental use, gel coats, photoresistsfor electronics, electroplating resists, etching resists, liquid and dryfilms, soldering resists; resists for producing color filters of variousdisplays or for forming structures in the production of plasma displaypanels, electroluminescent displays, and LCDs; encapsulatingcompositions for electric/electronic components, magnetic recordingmaterials, fine machine parts, waveguides, optical switches, platingmasks, etching masks, color test systems, glass fiber cable coatings,screen printing stencils, materials for making a three-dimensionalobject by stereolithography, holographic recording materials, imagerecording materials, fine electronic circuits, decolorizing materials,decolorizing materials for image recording materials, decolorizingmaterials for image recording materials using microcapsules, photoresistmaterials for printed wiring boards, photoresist materials for directimage writing using UV and visible lasers, and photoresist materials orprotective layers used to form dielectric layers in the fabrication ofmultilayered printed circuit boards.

The photosensitive composition containing the oxime ester compound ofthe invention can be cured with active light from light sources emittinglight of wavelengths of from 300 to 450 nm. Such light sources includean ultrahigh pressure mercury lamps, mercury vapor arcs, carbon arcs,and xenon arcs.

EXAMPLES

The present invention will now be illustrated in greater detail withreference to Examples, but it should be understood that the invention isnot deemed to be limited thereto.

Examples 1-1 to 1-22 Preparation of Compound Nos. 1 to 3, 7, 10, 12, 20,33, 45 to 51, and 53 to 58 Step 1-Preparation of Acylated Compound

In a nitrogen atmosphere, 10.4 g (78 mmol) of aluminum chloride and 33.0g of dichloroethane were put in a reactor. In the same atmosphere, 36mmol of an acid chloride and then 30 mmol of a nitrocarbazole compoundand 33.0 g of dichloroethane were added slowly while cooling with ice,followed by stirring at 5° C. for 30 minutes. The reaction mixture waspoured into ice-water for oil-water separation. The solvent was removedto give a desired acylated compound.

Step 2-Preparation of Compound Nos. 1 to 3, 7, 10, 12, 20, 33, 45 to 51,and 53 to 58

In a reactor were charged 20 mmol of the acylated compound obtained instep (1), 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g ofdimethylformamide and stirred at 80° C. for 1 hour in a nitrogen stream.The reaction system was cooled to room temperature, followed byoil-water separation. The solvent was removed by evaporation. To theresidue were added 25.4 g of butyl acetate and then 2.45 g (24 mmol) ofacetic anhydride. The mixture was stirred at 90° C. for 1 hour, followedby cooling to room temperature. The reaction mixture was neutralizedwith a 5% sodium hydroxide aqueous solution, followed by oil-waterseparation, followed by solvent removal, followed by recrystallizationfrom ethyl acetate to yield compound Nos. 1 to 3, 7, 10, 12, 20, 33, 45to 51, and 53 to 58. The analytical results of the resulting compoundsare shown in Tables 1 to 3. With respect to compound No. 49, two isomerswere separately isolated so that analytical results for each of them areshown. With respect to compound Nos. 53 and 54, the isomers gavedifferent results only in the NMR analysis as shown in Table 3.

TABLE 1 Oxime Ester Melting Decomp. Solubility Solubility Compoundλ_(max)*¹ (nm) Point (° C.) Point (° C.) PGM-Ac*² (%) CHN*³ (%) ExampleCompound 277,372 125.1 278.3 4.1 18.9 1-1 No. 1 Example Compound 272,373126.9 262.2 1.4 9.2 1-2 No. 2 Example Compound 272,371 204.9 263.9 0.120.80 1-3 No. 3 Example Compound 275,370 152.4 258.0 0.38 2.4 1-4 No. 7Example Compound 261,272,362 205.1 257.1 0.091 0.54 1-5 No. 10 ExampleCompound 275,372 67.3 281.0 25 31 1-6 No. 12 Example Compound 273,365158.0 264.3 0.16 3.7 1-7 No. 20 Example Compound 280,372 140.9 272.8 5.127 1-8 No. 33 Example Compound 272,374 107.2 277.8 0.4 7.2 1-9 No. 45Example Compound 271,374 92.7 261.3 0.5 5.0 1-10 No. 46 Example Compound275,373 98.1 271.7 0.3 5.3 1-11 No. 47 Example Compound 275,374 85.5245.9 5.0 42 1-12 No. 48 Example Compound 279,378 176.1 277.4 0.49 5.31-13 No. 49(1) Example Compound 279,369 150.9 288.2 1.0 6.8 1-14 No.49(2) Example Compound 276,373 77.3 248.5 6.0 45 1-15 No. 50 ExampleCompound 267,373 142.4 256.6 1.5 13 1-16 No. 51 Example Compound 276,378147.1 280.1 5.0 24 1-17 No. 53 Example Compound 279,373 oil 258.9 20 141-18 No. 54 Example Compound 283,373 152.5 302.4 1.2 3.2 1-19 No. 55Example Compound 282,375 137.1 283.5 3.6 23 1-20 No. 56 Example Compound280,373 164.0 275.5 2.4 12 1-21 No. 57 Example Compound 283,372 153.4269.3 1.2 7.6 1-22 No. 58 *¹CHCl₃ was used as a solvent. *²PGM-Ac:Propylene glycol-1-monomethyl ether-2-acetate *³CHN: Cyclohexane

TABLE 2 Oxime Ester Compound IR Absorption Spectrum (cm⁻¹) ExampleCompound 2958, 2930, 2872, 1766, 1631, 1600, 1513, 1485, 1459, 1366,1328, 1223, 1203, 1-1 No. 1 1152, 1135, 1092, 984, 931, 879, 823, 749,728 Example Compound 2928, 2858, 1765, 1633, 1600, 1506, 1488, 1368,1323, 1203, 1153, 1137, 1092, 1-2 No. 2 984, 930, 883, 822, 807, .751,727, 648 Example Compound 2980, 1766, 1630, 1599, 1488, 1458, 1377,1339, 1316, 1277, 1209, 1200, 1152, 1-3 No. 3 1130, 1094, 1004, 983,935, 912, 884, 806, 750, 717, 645 Example Compound 2971, 2864, 1769,1600, 1509, 1487, 1362, 1321, 1266, 1223, 1156, 1330, 1114, 1-4 No. 71094, 1049, 1021, 931, 888, 843, 811, 750, 717 Example Compound 2941,1762, 1744, 1630, 1601, 1508, 1489, 1459, 1375, 1330, 1308, 1205, 1159,1-5 No. 10 1136, 1096, 1009, 984, 888, 819, 751, 729 Example Compound3090, 2979, 2935, 2360, 2342, 1765, 1732, 1631, 1599, 1513, 1487, 1458,1368, 1-6 No. 12 1330, 1263, 1203, 1155, 1136, 1094, 1004, 983, 936,885, 817, 751, 728 Example Compound 2924, 2851, 1764, 1719, 1635, 1604,1513, 1484, 1458, 1410, 1362, 1321, 1303, 1-7 No. 20 1200, 1136, 1092,1005, 943, 886, 864, 816, 747, 728, 682 Example Compound 2979, 1765,1604, 1514, 1484, 1365, 1328, 1275, 1234, 1201, 1096, 1006, 922, 1-8 No.33 823, 751, 649 Example Compound 2923, 2850, 1766, 1627, 1596, 1580,1511, 1486, 1468, 1427, 1363, 1330, 1290, 1-9 No. 45 1238, 1224, 1198,1154, 1133, 1092, 1000, 982, 933, 903, 884, 819, 752, 727 ExampleCompound 2925, 2851, 1759, 1627, 1597, 1583, 1509, 1487, 1469, 1365,1325, 1226, 1207, 1-10 No. 46 1156, 1134, 1092, 1043, 1004, 980, 936,913, 901, 882, 833, 817, 751, 728, 714 Example Compound 2918, 2849,1761, 1746, 1629, 1598, 1509, 1487, 1467, 1369, 1321, 1227, 1153, 1-11No. 47 1133, 1091, 1011, 939, 908, 887, 811, 751, 725 Example Compound2926, 2856, 1768, 1629, 1599, 1507, 1487, 1459, 1368, 1333, 1204, 1153,1135, 1-12 No. 48 1094, 1002, 934, 891, 819, 751 Example Compound 2930,1760, 1630, 1599, 1510, 1484, 1326, 1202, 1153, 1133, 1091, 1004, 922,1-13 No. 49(1) 824, 776, 752, 696 Example Compound 2960, 2930, 2866,1770, 1629, 1599, 1517, 1484, 1460, 1365, 1326, 1200, 1140, 1-14 No.49(2) 1090, 1008, 931, 898, 864, 823, 804, 778, 753, 734, 697 ExampleCompound 2918, 2853, 1766, 1600, 1507, 1486, 1334, 1211, 1152, 1094,1002, 936, 911, 1-15 No. 50 876, 825, 751, 715 Example Compound 2928,1764, 1750, 1630, 1599, 1505, 1487, 1456, 1365, 1332, 1218, 1204, 1153,1-16 No. 51 1134, 1092, 999, 957, 895, 879, 827, 751, 695 ExampleCompound 2961, 2871, 1765, 1630, 1600, 1513, 1483, 1364, 1330, 1204,1157, 1133, 1092, 1-17 No. 53 1004, 931, 843, 815, 752, 687 ExampleCompound 2929, 1768, 1602, 1508, 1484, 1329, 1250, 1201, 1155, 1092,1003, 930, 815, 1-18 No. 54 752, 732 Example Compound 2929, 1764, 1600,1510, 1484, 1329, 1203, 1132, 1091, 930, 753 1-19 No. 55 ExampleCompound 2931, 1753, 1607, 1509, 1483, 1328, 1199, 1121, 1091, 1043,926, 817, 752 1-20 No. 56 Example Compound 2979, 1764, 1509, 1484, 1329,1274, 1233, 1195, 1119, 1009, 944, 752 1-21 No. 57 Example Compound2960, 2930, 1764, 1601, 1515, 1484, 1365, 1329, 1198, 1159, 1133, 1092,1005, 1-22 No. 58 952, 918, 864, 819, 794, 752, 704, 644

TABLE 3 Oxime Ester Compound ¹H-NMR(CDCl₃) Example Compound 0.85 (t,3H), 0.92 (t, 3H), 1.20-1.44 (m, 8H), 2.03 (dddddd, 1H), 2.32 (s, 3H),2.54 (s, 1-1 No. 1 3H), 4.21 (dd, 1H), 4.24 (dd, 1H), 7.42 (d, 1H), 7.46(d, 1H), 8.06 (dd, 1H), 8.40 (dd, 1H), 8.49 (d, 1H), 9.04 (d, 1H)Example Compound 0.85 (t, 3H), 1.18-1.39 (m, 10H), 1.84-1.91 (m, 2H),2.32 (s, 3H), 2.53 (s, 3H), 4.33 1-2 No. 2 (t, 2H), 7.41 (d, 1H), 7.45(d, 1H), 8.04 (dd, 1H), 8.37 (dd, 1H), 8.46 (d, 1H), 8.99 (dd, 1H)Example Compound 1.49 (t, 3H), 2.32 (t, 3H), 2.54 (s, 3H), 4.43 (q, 2H),7.43 (d, 1H), 7.47 (d, 1H), 8.06 1-3 No. 3 (dd, 1H), 8.39 (dd, 1H), 8.48(d, 1H), 9.01 (d, 1H) Example Compound 1.06 (t, 3H), 2.32 (t, 3H), 2.55(s, 3H), 3.39 (q, 2H), 3.83 (t, 2H), 4.54 (t, 2H), 7.39 (d, 1-4 No. 72H), 8.06 (dd, 1H), 8.39 (dd, 1H), 8.49 (d, 1H), 9.04 (d, 1H) ExampleCompound 1.22 (t, 3H), 2.32 (t, 3H), 2.54 (s, 3H), 3.29 (s, 3H), 3.37(d, 1H), 3.38 (d, 1H), 5.09 1-5 No. 10 (s, 2H), 5.20 (ddq, 1H), 7.39 (d,1H), 7.42 (d, 1H), 8.06 (dd, 1H), 8.41(d, 1H), 8.50 (d, 1H), 9.05 (d,1H) Example Compound 1.18 (d, 3H), 1.42 (tt, 2H), 1.69 (tt, 2H), 1.92(tt, 2H), 2.30 (t, 2H), 2.32 (s, 3H), 2.54 1-6 No. 12 (s, 3H), 3.34 (s,3H), 3.37 (dd, 1H), 3.39 (dd, 1H), 4.37 (t, 2H), 5.07 (ddq, 2H), 7.44(d, 1H), 7.46 (d, 1H), 8.06 (dd, 1H), 8.40 (dd, 1H), 8.50 (dd, 1H), 9.04(dd, 1H) Example Compound 0.86 (t, 3H), 1.21-1.68 (m, 18H), 2.31 (s,3H), 2.99 (t, 2H), 4.59 (t, 2H), 4.69 (t, 2H), 1-7 No. 20 5.80 (dd, 1H),5.97 (dd, 1H), 6.27 (dd, 1H), 7.50 (d, 1H), 7.52 (d, 1H), 8.02 (dd, 1H),8.41 (dd, 1H), 8.47 (d, 1H), 9.05 (d, 1H) Example Compound 1.42 (d, 3H),1.47 (t, 3H), 2.11 (s, 3H), 2.15 (s, 3H), 3.47 (s, 3H), 3.55 (dd, 1H),3.67 1-8 No. 33 (dd, 1H), 4.43 (q, 2H), 4.67 (ddq, 1H), 6.88 (dd, 1H),6.93 (d, 1H), 7.05 (d, 1H), 7.43 (d, 1H), 7.46 (d, 1H), 8.05 (dd, 1H),8.17 (d, 1H), 8.39 (dd, 1H), 8.95 (d, 1H) Example Compound 0.87 (t, 3H),1.22-1.33 (m, 18H), 1.87 (tt, 2H), 2.31 (s, 3H), 2.54 (s, 3H), 4.35 (t,2H), 1-9 No. 45 7.43 (d, 1H), 7.46 (d, 1H), 8.06 (dd, 1H), 8.40 (dd,1H), 8.49 (d, 1H), 9.04 (d, 1H) Example Compound 0.87 (t, 3H), 1.23-1.38(m, 22H), 1.89 (tt, 2H), 2.32 (s, 3H), 2.54 (s, 3H), 4.36 (t, 2H), 1-10No. 46 7.44 (d, 1H), 7.47 (d, 1H), 8.06 (dd, 1H), 8.41 (dd, 1H), 8.50(d, 1H), 9.05 (d, 1H) Example Compound 0.87 (t, 3H), 1.22-1.33 (m, 26H),1.89 (tt, 2H), 2.31 (s, 3H), 2.54 (s, 3H), 4.36 (t, 2H), 1-11 No. 477.44 (d, 1H), 7.47 (d, 1H), 8.06 (dd, 1H), 8.41 (dd, 1H), 8.50 (d, 1H),9.06 (d, 1H) Example Compound 0.84-0.96 (m, 9H), 1.25-1.69 (m, 18H),2.05 (dddddd, 1H), 2.32 (s, 3H), 3.00 (t, 2H), 1-12 No. 48 4.24 (d, 2H),7.43 (d, 1H), 7.47 (d, 1H), 8.02 (dd, 1H), 8.40 (dd, 1H), 8.47 (d, 1H),9.06 (d, 1H) Example Compound 0.85 (t, 3H), 0.92 (t, 3H), 1.22-1.43 (m,8H), 2.03 (dddddd, 1H), 2.13 (s, 3H), 4.23 (d, 1-13 No. 49(1) 2H),7.38-7.45 (m, 4H), 7.51-7.55 (m, 3H), 7.97 (dd, 1H), 8.19 (s, 1H), 8.37(dd, 1H), 8.91 (d, 1H) Example Compound 0.88 (t, 3H), 0.98 (t, 3H),1.24-1.50 (m, 8H), 2.11 (dddddd, 1H), 2.17 (s, 3H), 4.27 (d, 1-14 No.49(2) 2H), 7.38-7.45 (m, 4H), 7.51-7.55 (m, 3H), 8.13 (d, 1H), 8.41 (dd,1H), 8.96 (d, 1H) Example Compound 0.85 (t, 3H), 0.86 (t, 3H), 0.93 (t,3H), 1.16-1.50 (m, 24H), 1.56-1.70 (m, 2H), 2.04 1-15 No. 50 (dddddd,1H), 2.30 (s, 3H), 2.98 (t, 2H), 4.21 (d, 2H), 7.42 (d, 1H), 7.46 (d,1H), 8.01 (dd, 1H), 8.40 (dd, 1H), 8.46 (d, 1H), 9.05 (d, 1H) ExampleCompound 0.84 (t, 3H), 0.91 (t, 3H), 1.16-1.46 (m, 8H), 2.01 (dddddd,1H), 2.26 (s, 3H), 4.20 (d, 1-16 No. 51 2H), 4.39 (s, 2H), 7.17-7.33 (m,5H), 7.39 (d, 1H), 7.42 (d, 1H), 8.02 (dd, 1H), 8.38 (dd, 1H), 8.51 (d,1H), 8.98 (d, 1H) Example Compound (1): 0.87 (t, 3H), 0.92 (t, 3H),1.27-1.52 (m, 8H), 1.42 (s, 9H), 1.98-2.14 (m, 1H), 1-17 No. 53 2.17 (s,3H), 4.23 (d, 2H), 7.16-7.58 (m, 6H), 7.95 (dd, 1H), 8.22 (d, 1H), 8.38(dd, 1H), 8.94 (d, 1H) (2): 0.85 (t, 3H), 0.97 (t, 3H), 1.27-1.52 (m,8H), 1.34 (s, 9H), 1.98-2.14 (m, 1H), 2.15 (s, 3H), 4.27 (d, 2H), 7.16-(1)/(2) = 52/48 Example Compound (1): 0.87 (t, 3H), 0.97 (t, 3H),1.22-1.46 (m, 8H), 1.34 (d, 3H), 2.01-2.14 (m, 1H), 1-18 No. 54 2.12 (s,3H), 3.41 (s, 3H), 3.51 (dd, 1H), 3.59 (dd, 1H), 4.26 (d, 2H), 4.61(ddq, 1H), 6.92 (ddd, 2H), 7.41 (d, 1H), 7.45 (d, 1H), 7.54 (ddd, 2H),7.58 (dd, 1H), 8.10 (d, 1H), 8.38 (dd, 1H), 8.97 (d, 1H) (2): 0.85 (t,3H), 0.92 (t, 3H), 1.22-1.46 (m, 8H), 1.41 (d, 3H), 2.01-2.14 (m, 1H),2.17 (s, 3H), 3.46 (s, 3H), 3.55 (dd, 1H), 3.66 (dd, 1H), 4.23 (d, 2H),4.68 (ddq, 1H), 7.04 (ddd, 2H), 7.36 (ddd, 2H), 7.44 (d, 1H), 7.51 (d,1H), 7.95 (dd, 1H), 8.21 (d, 1H), 8.41 (dd, 1H), 8.95 (d, 1H) (1)/(2) =53/47 Example Compound 0.85 (t, 3H), 0.92 (t, 3H), 1.19-1.46 (m, 8H),2.03 (dddddd, 1H), 2.10 (s, 3H), 3.18 (s, 1-19 No. 55 3H), 3.50 (t, 2H),4.10 (t, 2H), 4.21 (dd, 1H), 4.23 (dd, 1H), 7.09 (dd, 1H), 7.11 (dd,1H), 7.18 (dd, 1H), 7.40 (d, 1H), 7.42 (d, 1H), 7.50 (ddd, 1H), 8.02(dd, 1H), 8.19 (d, 1H), 8.37 (dd, 1H), 8.91 (d, 1H) Example Compound0.86 (t, 3H), 0.93 (t, 3H), 1.16 (t, 3H), 1.21-1.49 (m, 8H), 1.51 (t,3H), 2.05 (dddddd, 1-20 No. 56 1H), 2.14(s, 3H), 3.99 (q, 2H), 4.15 (q,2H), 4.23 (dd, 1H), 4.25 (dd, 1H), 6.60 (dd, 1H), 6.61 (d, 1H), 7.10 (d,1H), 7.41 (d, 1H), 7.43 (d, 1H), 8.06 (dd, 1H), 8.18 (d, 1H), 8.38 (dd,1H), 8.94 (d, 1H) Example Compound 1.12 (d, 6H), 1.44 (d, 6H), 1.49 (t,3H), 2.13 (s, 3H), 4.43 (q, 2H), 4.48 (sep, 1H), 1-21 No. 57 4.65 (sep,1H), 6.56 (dd, 1H), 6.56 (d, 1H), 7.06 (d, 1H), 7.42 (d, 1H), 7.44 (d,1H), 8.02 (dd, 1H), 8.19 (d, 1H), 8.39 (dd, 1H), 8.94 (d, 1H) ExampleCompound 0.85 (t, 3H), 0.92 (t, 3H), 1.21-1.46 (m, 8H), 2.03 (dddddd,1H), 2.10 (s, 3H), 2.20 (s, 1-22 No. 58 3H), 4.23 (d, 2H), 7.05 (ddd,1H), 7.10 (dd, 1H), 7.14 (dd, 1H), 7.41 (d, 1H), 7.44 (d, 1H), 8.02 (dd,1H), 8.13 (d, 1H), 8.38 (dd, 1H), 8.93 (d, 1H)

Example 2 Preparation of Photosensitive Composition No. 1

To 14.0 g of an acrylic copolymer were added 5.90 g oftrimethylolpropane triacrylate, 2.70 g of compound No. 1 obtained inExample 1-1, and 79.0 g of ethyl cellosolve, and the mixture wasthoroughly stirred to obtain photosensitive composition No. 1.

The acrylic copolymer used above was obtained by dissolving 20 parts bymass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate,10 parts by mass of methyl methacrylate, and 55 parts by mass of butylmethacrylate in 300 parts by mass of ethyl cellosolve, adding thereto0.75 parts by mass of azobisisobutyronitrile, followed by heating at 70°C. for 5 hours in a nitrogen atmosphere.

Example 3 Preparation of Photosensitive Composition No. 2

Photosensitive composition No. 2 was obtained in the same manner as inExample 2, except for replacing compound No. 1 prepared in Example 1-1with 2.70 g of compound No. 2 prepared in Example 1-2.

Example 4 Preparation of Photosensitive Composition No. 3

Photosensitive composition No. 3 was obtained in the same manner as inExample 2, except for replacing compound No. 1 prepared in Example 1-1with 2.70 g of compound No. 3 prepared in Example 1-3.

Example 5 Preparation of Photosensitive Composition No. 4

Photosensitive composition No. 4 was obtained in the same manner as inExample 2, except for replacing compound No. 1 prepared in Example 1-1with 2.70 g of compound No. 7 prepared in Example 1-4.

Example 6 Preparation of Photosensitive Composition No. 5

Photosensitive composition No. 5 was obtained in the same manner as inExample 2, except for replacing compound No. 1 prepared in Example 1-1with 2.70 g of compound No. 10 prepared in Example 1-5.

Example 7 Preparation of Photosensitive Composition No. 6

Photosensitive composition No. 6 was obtained in the same manner as inExample 2, except for replacing compound No. 1 prepared in Example 1-1with 2.70 g of compound No. 12 prepared in Example 1-6.

Example 8 Preparation of Photosensitive Composition No. 7

Dipentaerythritol pentaacrylate (15.0 g) and 3.74 g of 1,4-butanedioldiglycidyl ether were mixed, and 3.30 g of compound No. 1 obtained inExample 1 and 78 g of ethyl cellosolve were added thereto, followed bythoroughly stirring to make photosensitive composition No. 7.

Example 9 Preparation of Photosensitive Composition No. 8 asAlkali-Developable Photosensitive Resin Composition Step 1-Preparationof Alkali Developable Resin Composition No. 8

In a reactor were put 17.0 g of1,1-bis(4′-epoxypropyloxyphenyl)-1-(1″-biphenyl)-1-cyclohexylmethane,4.43 g of acrylic acid, 0.06 g of 2,6-di-tert-butyl-p-cresol, 0.11 g oftetrabutylammonium acetate, and 14.3 g of propylene glycol-1-monomethylether-2-acetate and stirred at 120° C. for 16 hours. The reaction systemwas cooled room temperature, and 7.18 g of propylene glycol-1-monomethylether-2-acetate, 4.82 g of succinic anhydride, and 0.25 g oftetrabutylammonium acetate, were added thereto, followed by stirring at100° C. for 5 hours. To the mixture were further added 5.08 g of1,1-bis(4′-epoxypropyloxyphenyl)-1-(1″-biphenyl)-1-cyclohexylmethane and2.18 g of propylene glycol-1-monomethyl ether-2-acetate, and the mixturewas stirred at 120° C. for 12 hours, 80° C. for 2 hours, and 40° C. for2 hours. Finally, 13.1 g of propylene glycol-1-monomethylether-2-acetate was added to give alkali developable resin compositionNo. 8 in the form of a propylene glycol-1-monomethyl ether-2-acetatesolution (Mw=4200; Mn=2100; acid value (solid basis): 55 mg-KOH/g).

Step 2-Preparation of Photosensitive Composition No. 8

Alkali developable resin composition No. 8 obtained in step 1 above(2.68 g), 0.73 g of trimethylolpropane triacrylate, 7.91 g of propyleneglycol-1-monomethyl ether-2-acetate, and 5.18 g of cyclohexanone weremixed. Compound No. 1 obtained in Example 1 (1.58 g) was added thereto,followed by stirring well to give photosensitive composition No. 8 as analkali developable photosensitive resin composition.

Example 10 Preparation of Photosensitive Composition No. 9 asAlkali-Developable Photosensitive Resin Composition Step 1-Preparationof Alkali Developable Resin Composition No. 9

In a reactor were put 184 g of a bisphenol fluorene epoxy resin (epoxyequivalent: 231), 58.0 g of acrylic acid, 0.26 g of2,6-di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and23.0 g of propylene glycol-1-monomethyl ether-2-acetate and stirred at120° C. for 16 hours. After cooling to room temperature, 35.0 g ofpropylene glycol-1-monomethyl ether-2-acetate, 59.0 g of biphthalicanhydride, and 0.24 g of tetra-n-butylammonium bromide were added to thereaction system, followed by stirring at 120° C. for 4 hours. To themixture were further added 20 g of tetrahydrophthalic anhydride, and themixture was stirred at 120° C. for 4 hours, 100° C. for 3 hours, 80° C.for 4 hours, 60° C. for 6 hours, and 40° C. for 11 hours. Finally, 90.0g of propylene glycol-1-monomethyl ether-2-acetate was added to givealkali developable resin composition No. 9 in the form of a propyleneglycol-1-monomethyl ether-2-acetate solution (Mw=5000; Mn=2100; acidvalue (solid basis): 92.7 mg-KOH/g).

Step 2-Preparation of Photosensitive Composition No. 9

Alkali developable resin composition No. 9 obtained in step 1 above(2.68 g), 0.73 g of trimethylolpropane triacrylate, 7.91 g of propyleneglycol-1-monomethyl ether-2-acetate, and 5.18 g of cyclohexanone weremixed. Compound No. 1 obtained in Example 1 (1.58 g) was added theretoto give photosensitive composition No. 9 as an alkali developablephotosensitive resin composition.

Example 11 Preparation of Photosensitive Composition No. 10 as ColoredAlkali-Developable Photosensitive Resin Composition

Photosensitive composition No. 10, which was a coloredalkali-developable photosensitive resin composition, was prepared in thesame manner as in Example 9, except for further adding 2.00 g of pigmentblue 15.

Example 12 Preparation of Photosensitive Composition No. 11 as ColoredAlkali-Developable Photosensitive Resin Composition

Photosensitive composition No. 11, which was a coloredalkali-developable photosensitive resin composition, was prepared in thesame manner as in Example 10, except for further adding 3.00 g of carbonblack.

Example 13 Preparation of Photosensitive Composition No. 12

Photosensitive composition No. 12 was prepared in the same manner as inExample 2, except for further adding 4.52 g of titanium oxide.

Comparative Example 1 Preparation of Photosensitive Composition No. 13

Photosensitive resin composition No. 13 for comparison was prepared inthe same manner as in Example 2, except for replacing compound No. 1obtained in Example 1-1 with 2.70 g of comparative compound 1 shownbelow.

Comparative Example 2 Preparation of Photosensitive Composition No. 14as Alkali Developable Photosensitive Resin Composition

Photosensitive resin composition No. 14 as a comparative alkalidevelopable photosensitive resin composition was prepared in the samemanner as in Example 9, except for replacing 1.58 g of compound No. 1obtained in Example 1-1 with 1.58 g of comparative compound 1.

Photosensitive composition No. 1 and photosensitive composition No. 13for comparison were tested for hardness as follows. The results obtainedare shown in Table 4.

Photosensitive composition No. 8, which was an alkali developablephotosensitive resin composition, and photosensitive resin compositionNo. 14, which was an alkali developable photosensitive resin compositionfor comparison, were evaluated for sensitivity as follows. The resultsare shown in Table 5.

Hardness Test

The photosensitive composition was applied to a 50 μm thick polyethyleneterephthalate film with a #3 bar coater and irradiated with light of ahigh pressure mercury lamp (80 W/cm) using a light irradiator equippedwith a belt conveyor. The distance between the lamp and the beltconveyor was 10 cm. The linear speed of the belt conveyor was 8 cm/min.After the thus cured coating layer was left to stand at room temperaturefor 24 hours, the hardness was measured using a pencil hardness testerunder a load of 1 kg.

Sensitivity

The alkali developable photosensitive resin composition was applied toan aluminum plate with a #3 bar coater to a thickness of about 1 μm,prebaked at 60° C. for 15 minutes, and exposed to light of an ultra-highpressure mercury lamp using a spectrophotometer CT-25CP form JASCO Corp.The exposed coating layer was dipped in a 2.5 mass % solution of sodiumcarbonate at 25° C., followed by thoroughly washing with water. Thespectral sensitivity at 365 nm and 405 nm was evaluated in terms of theminimum energy of light at 365 nm and 405 nm necessary for the coatinglayer to sufficiently cure to remain on the aluminum plate.

TABLE 4 Photosensitive Composition Pencil Hardness No. 1 (Example 2) 3HNo. 13 (Comparative Example 1) 1H

TABLE 5 Sensitivity (mJ/cm²) Photosensitive Composition 365 nm 405 nmNo. 8 (Example 9) 5.9 2.4 No. 14 (Comp. Example 2) 18.6 762

Photosensitive composition No. 1 of Example 2 gained high hardness oncuring, whereas photosensitive composition No. 13 of Comparative Example1 failed to provide sufficient hardness. Alkali developablephotosensitive resin composition No. 8 of Example 9 exhibited highsensitivity to light of long wavelengths, i.e., 365 nm and 405 nm,whereas alkali developable photosensitive resin composition No. 14 ofComparative Example 2 required an increased amount of energy forexposure at 365 nm and 405 nm on account of low sensitivity to thesewavelengths of light.

Example 14 Preparation of Photosensitive Composition No. 15 as ColoredAlkali Developable Photosensitive Resin Composition

Alkali developable resin composition No. 8 obtained in step 1 of Example9 (11.5 g), 0.3 g of a mixture of dipentaerythritol pentaacrylate anddipentaerythritol hexaacrylate, 6.6 g of carbon black, 30.0 g ofpropylene glycol-1-monomethyl ether-2-acetate, and 30.0 g ofcyclohexanone were mixed. Compound No. 54 obtained in Example 1-17 (1.0g) was added thereto, followed by stirring well to give photosensitivecomposition No. 15 as a colored alkali developable photosensitive resincomposition.

Comparative Example 3 Preparation of Photosensitive Composition No. 16as Colored Alkali Developable Photosensitive Resin Composition

Photosensitive composition No. 16 as a comparative coloredalkali-developable photosensitive resin composition was prepared in thesame manner as in Example 14, except for replacing compound No. 54obtained in Example 1-17 with 1.0 g of comparative compound 1.

Photosensitive composition No. 15 and comparative photosensitivecomposition No. 16 were evaluated as follows. The results obtained areshown in Table 6.

The colored alkali-developable photosensitive resin composition wasapplied to a glass substrate by spin coating at 900 rpm for 10 secondsand prebaked at 70° C. for 20 minutes. The coating film was exposed tolight from a high pressure mercury lamp through a mask of prescribedpattern, dipped in a 2.5 mass % aqueous solution of sodium carbonate at25° C. for 40 seconds, followed by thoroughly washing with water. Afterdrying, the thus developed coating film was baked at 230° C. for 1 hourto fix the pattern. The resulting pattern was evaluated as follows.

Sensitivity

A photosensitive composition that succeeded in patterning with anexposure energy of 60 mJ/cm² was graded A. A photosensitive compositionthat failed to form a pattern until the exposure energy was raised to100 mJ/cm² or 150 mJ/cm² was graded B or C, respectively.

Resolution

A photosensitive composition that succeeded in forming a satisfactorypattern of a line width of 8 μm or less was graded A. A photosensitivecomposition that succeeded in forming a good pattern with a line widthof from 10 to 30 μm was graded B. A photosensitive composition thatsucceeded to form a good pattern with a line width of 30 μm or more wasgraded C.

Adhesion

The pattern formed by the development was inspected for peeling. Apattern suffering from no peeling was rated “good”, while a patternsuffering from peeling in part was rated “poor”.

TABLE 6 Photosensitive Composition Sensitivity Resolution Adhesion No.15 (Example 14) A A good No. 16 (Comp. C C poor Example 3)The photosensitive composition 15 of Example 14, which was a colored,alkali-developable photosensitive resin composition, exhibited highsensitivity and high resolution and provided a cured film with highadhesion to the substrate and no peeling. In contrast, photosensitivecomposition 16 of Comparative Example 3, which was a colored,alkali-developable photosensitive resin composition, had lowsensitivity, low resolution, and poor adhesion to the substrate.

INDUSTRIAL APPLICABILITY

The oxime ester compound of the invention exhibits highphotosensitivity, particularly to long wavelengths of light at 365 nm(i-rays) and 405 nm (h-rays), and is therefore useful as aphotopolymerization initiator.

1. An oxime ester compound represented by general formula (I):

wherein R¹, R², and R³ each independently represent R¹¹, OR¹¹, COR¹¹, SR¹¹, CONR¹²R¹³, or CN; R¹¹, R¹², and R¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, in which the alkyl group, aryl group, arylalkyl group, and heterocyclic group may have their hydrogen atom substituted with OR²¹, COR²¹, SR²¹, NR²²R²³, CONR²²R²³, —NR²²—OR²³, —NCOR²²—OCOR²³, —C(═N—OR²¹)—R²², —C(═N—OCOR²¹)—R²², CN, a halogen atom, —CR²¹═CR²²R²³, —CO—CR²¹═CR²²R²³, a carboxyl group, or an epoxy group; R²¹, R²², and R²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; the methylene units of the alkylene moiety of the substituents represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³ may be interrupted by an unsaturated linkage, an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, or a urethane linkage at 1 to 5 sites thereof; the alkyl moiety of the substituents represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³ may be branched or cyclic; an alkyl terminal of the substituents represented by R¹¹, R¹², R¹³, R²¹, R²², and R²³ may have an unsaturated bond; R¹² and R¹³, and R²² and R²³ may be connected to each other form a ring; R³ may be taken together with a neighboring benzene ring; R⁴ and R⁵ each independently represent R¹¹, OR¹¹, SR¹¹, COR¹¹, CONR¹², R¹³, NR¹²COR¹¹, OCOR¹¹, COOR¹¹, SCOR¹¹, OCSR¹¹, COSR¹¹, CSOR¹¹, CN, a halogen atom, or a hydroxyl group; and a and b each independently represent 0 to
 3. 2. The oxime ester compound according to claim 1, wherein R¹ is an alkyl group having 11 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, OR¹¹, COR¹¹, SR¹¹, CONR¹²R¹³, or CN; or R³ is an alkyl group having 1 to 12 carbon atoms interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof, an alkyl group having 13 to 20 carbon atoms, OR¹¹, COR¹¹, SR¹¹, CONR¹²R¹³, or CN; and R¹¹, R¹², and R¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; the alkyl group, aryl group, arylalkyl group, and heterocyclic group as represented by R¹, R³, R¹¹, R¹², and R¹³ may have their hydrogen atom substituted with OR²¹, COR²¹, SR²¹, NR²²R²³, CONR²²R²³, —NR²²—OR²³, —NCOR²²—OCOR²³, —C(═N—OR²¹)—R²², —C(═N—OCOR²¹)—R²², CN, a halogen atom, —CR²¹═CR²²R²³, —CO—CR²¹═CR²²R²³, a carboxyl group, or an epoxy group; R²¹, R²², and R²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; the methylene units of the alkylene moiety of the substituents represented by R¹, R³, R₁₁, R¹², R¹³, R²¹, R²², and R²³ may be interrupted by an unsaturated linkage, an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, or a urethane linkage at 1 to 5 sites thereof; the alkyl moiety of the substituents represented by R¹, R³, R₁₁, R¹², R¹³, R²¹, R²², and R²³ may be branched or cyclic; the alkyl terminal of the substituents represented by R¹, R³, R₁₁, R¹², R¹³, R²¹, R²², and R²³ may have an unsaturated bond; R¹² and R¹³ may be connected to form a ring; and R³ may be taken together with a neighboring benzene ring.
 3. The oxime ester compound according to claim 1, wherein R¹ is an alkyl group having 11 to 20 carbon atoms or an aryl group with 6 to 30 carbon atoms; the alkyl group and the aryl group as represented by R¹ may have their hydrogen atom substituted with OR²¹ COR²¹, SR²¹, NR²² _(R) ²³, CONR²²R²³, —NR²²—OR²³, —NCOR²²—OCOR²³, —C(═N—OR²¹)—R²², —C(═N—OCOR²¹)—R²², CN, a halogen atom, —CR²¹═CR²²R²³, —CO—CR²¹═CR²²R²³, a carboxyl group, or an epoxy group; _(R) ²¹, R²², and R²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; the methylene units of the alkylene moiety of the substituents represented by R¹, R²¹, R^(22,) , and R²³ may be interrupted by an unsaturated linkage, an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, or a urethane linkage at 1 to 5 sites thereof; the alkyl moiety of the substituents represented by R¹, R²¹, R²², and R²³ may be branched or cyclic; the alkyl terminal of the substituents represented by R¹, R²¹, R²², and R²³ may have an unsaturated bond.
 4. The oxime ester compound according to claim 1, wherein R³ is a branched alkyl group having 8 or more carbon atoms the methylene units of which may be interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof.
 5. The oxime ester compound according to claim 1, wherein R³ is an alkyl group having 13 or more carbon atoms the methylene units of which may be interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof.
 6. The oxime ester compound according to claim 1, wherein R³ is an alkyl group interrupted by an ether linkage at 1 to 5 sites thereof.
 7. The oxime ester compound according to claim 1, wherein R³ is an alkyl group interrupted by an ester linkage at 1 to 5 sites thereof.
 8. The oxime ester compound according to claim 1, which dissolves in propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone to a concentration of 1% by mass or more.
 9. A photopolymerization initiator comprising the oxime ester compound according to claim 1 as an active ingredient.
 10. A photosensitive composition comprising the photopolymerization initiator according to claim 9 and a polymerizable compound having an ethylenically unsaturated bond.
 11. The photosensitive composition according to claim 10, further comprising an inorganic compound.
 12. An alkali-developable photosensitive resin composition comprising the photopolymerization initiator according to claim 9 and an alkali-developable compound having an ethylenically unsaturated compound.
 13. A colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition according to claim 9 and a colorant.
 14. The oxime ester compound according to claim 2, wherein R¹ is an alkyl group having 11 to 20 carbon atoms or an aryl group with 6 to 30 carbon atoms; the alkyl group and the aryl group as represented by R¹ may have their hydrogen atom substituted with OR²¹, COR²¹, SR²¹, NR²²R²³, CONR²²R²³, —NR²²—OR²³, —NCOR²²—OCOR²³, —C(═N—OR²¹)—R²², —C(═N-OCOR²¹)—R²², CN, a halogen atom, —CR²¹═CR²²R²³, —CO—CR²¹═CR²²R²³, a carboxyl group, or an epoxy group; R²¹, R²², and R²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; the methylene units of the alkylene moiety of the substituents represented by R¹, R²¹, R²², and R²³ may be interrupted by an unsaturated linkage, an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, or a urethane linkage at 1 to 5 sites thereof; the alkyl moiety of the substituents represented by R¹, R²¹, R²², and R²³ may be branched or cyclic; the alkyl terminal of the substituents represented by R¹, R²¹, R²², and R²³ may have an unsaturated bond.
 15. The oxime ester compound according to claim 2, wherein R³ is a branched alkyl group having 8 or more carbon atoms the methylene units of which may be interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof.
 16. The oxime ester compound according to claim 3, wherein R³ is a branched alkyl group having 8 or more carbon atoms the methylene units of which may be interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof.
 17. The oxime ester compound according to claim 2, wherein R³ is an alkyl group having 13 or more carbon atoms the methylene units of which may be interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof.
 18. The oxime ester compound according to claim 3, wherein R³ is an alkyl group having 13 or more carbon atoms the methylene units of which may be interrupted by an ether linkage or an ester linkage at 1 to 5 sites thereof.
 19. The oxime ester compound according to claim 2, wherein R³ is an alkyl group interrupted by an ether linkage at 1 to 5 sites thereof.
 20. The oxime ester compound according to claim 3, wherein R³ is an alkyl group interrupted by an ether linkage at 1 to 5 sites thereof. 